The influence of (H2O)1–2 in the HOBr + HO2 gas-phase reaction

Abstract

The HOBr + HO₂ reaction in the absence of water has three different channels for the abstraction of H to generate the corresponding products. The dominant channel is the generation of BrO + H₂O₂. The introduction of water molecules influences this dominant reaction via the way the reactants interact with the water molecules. The addition of water molecules decreases the energy barrier and increases the rate coefficient of the reaction. Interestingly, water works as a catalyst and we obtain BrO + H₂O₂, like in the reaction without water, or the water works as a reactant and we obtain products other than BrO + H₂O₂. The rate coefficients of the HOBr + HO₂ reaction in the presence of water are calculated to be faster than the reaction in the absence of water. However, other pathways in the presence of water are slower than the reaction in the absence of water. The water-assisted effective rate coefficients for the HOBr + HO₂ reaction are also larger than those for the reaction in the absence of water. The influence of a water dimer is not as important when compared with one water molecule. In summary, a single water molecule has a positive catalytic influence in enhancing the HOBr + HO₂ reaction.